Treatment of rosin



Patented Feb. 16, 1943 TREATMENT OF ROSIN Laszl Auer, South Orange, N. J.

No Drawing.

Application October 12, 1942,

Serial No. 461,792

15 Claims.

GENERAL Fnztn or INVENTION AND STATEMENT or OBJacTS This invention relates to treatment of rosin, and especially to treatment with certain modifying agents promoting softening or liquefaction of rosin. This application is a continuation-inpart of my application Serial No. 386,371, filed April 1, 1941.

As is known, gum or wood rosins contain mixtures of rosin acids, known today as abietic acid, pyro-abietic acid and d-pimaric acid amongst others. Such rosins commonly have an acid value of from about 145 to 185, usually from about 160 to about 168, and in their natural state they are ordinarily hard, brittle materials, of melting point from about 70 C. to about 85 C.

Rosin is a valuable raw material for a number of commercial purposes, such as in paper sizing, soap manufacture, and especially in the coatings and plastics industries. There are, in fact, a number of examples in the art of use of various rosin derivatives for purposes such as those mentioned. Some of the most important and common examples occur in the coatings industry, i. e., use of rosin derivatives in paints, varnishes and the like.

In its natural state, however, rosin is not well ing drying or film forming characteristics which are well suited to the coating composition industry, thereby even making possible employment of the modified rosin products alone as vehicle solids in varnishes and the like. Usually, however, at least some drying or semi-drying oil is advantageously used with the modified products.

suited to many commercial purposes for which it is potentially a valuable raw material.

The primary object of the present. invention is to modify various physical properties of rosin, whereby to produce modified rosin products which are better adapted to many uses for which rosin or rosin derivatives are now employed. In

addition, the modifications brought about'in accordancev with the present invention make it possible and advantageous to use the modified rosin products for many purposes for which rosin in its natural state and also various derivatives thereof are not well suited.

To illustrate, reference is made to coating compositions, such as varnishes. In its natural state, rosin is a brittle material and therefore yields a brittle film when employedalone as varnish solids. Thus, rosin in its natural state does not have film forming characteristics such that it may satisfactorily be employed alone as vehicle solids in a coating composition. According to this invention modifications are brought about in the rosin so as to secure a rosin product hav- Because of the improved properties of the modified rosin products, such products may be employed as a replacement ingredient, in substantial proportions, for linseed or other drying or semi-drying oils in paints and other coating and plastic compositions.

For certain special purposes in the soap and paper sizing industries, the modified rosin products of this invention may also be of advantage, notwithstanding the fact that the modified products have a reduced acid value.

One of the most important modifications brought about by the process of the invention is the softening or liquefying of the rosin, i. e., at least some reduction of brittleness or in melting point, or both. In addition, the process of the invention is notable in its effect on the acid value, the invention providing for appreciable reduction in acid value, as will further appear. In referring to changes of this type and in making comparisons of the modified products with is often herein referred to as a blank or contro experiment;

According to the invention, by appropriate control of treatment conditions, and by appropriate selection of materials, the degree of softening or liquefaction and also of acid value may be regulated to meet various different requirements. For instance, according to the invention, it is possible to very extensively soften the rosin, or to very extensively lower the acid value,

or both. 7

' Although the invention is not limited thereto, it is of especial importance and advantage in accordance with the invention to subject the rosin to treatment for a time and under conditions such as to change the physical character of the rosin from its natural hard and brittle condition to a consistency approximating the so-called "cold flow, i. e., a consistency according to which the material'will gradually flow at normal room temperatures, so that if a blob of the modified rosin is placed on a flat surface, it will more or less gradually flatten out, often at a rate which is not observable with the eye. For many purposes a liquefaction at least to this degree is desirable.

For certain purposes it is advantageous that the rosin be liquefied even to the extent of becoming a mobile liquid, similar, for instance, to the consistency of certain oils, such as bodied linseed oil.

My preferred range of liquefaction extends from about the consistency of a viscous oil to about the cold flow consistency above mentioned, although it is to be understood that a greater or a lesser degree of liquefaction is also contemplated.

' Tm: MODIFICATION PROCESS The process of the invention involves heating the rosin in the presence of a modifying agent of the type mentioned hereinafter, the duration of heating, temperature and other treatment conditions, as more fully explained here below, being controlled in accordance with the extent and type of modification desired.

In general, modifying agents employed in accordance with this invention, and also in accordance with certain of my copending applications, identified hereinafter, are polar compounds. The present application is particularly directed to the use of salts of the alkali metals and of ammonium (which latter acts similarly to the former), as modifying agents for rosin.

Metal salts of this class, especially certain groups thereof such as carbonates, sulphides and sulphites (which release a gas other than oxygen under the conditions of the treatment), are useful agents in effecting modification of physical properties of rosin, and especially in effecting reduction both in acid value and in melting point. As will be pointed out more fully hereinafter, use of certain salts in the class to which this application is directed, enables production of modified rosin products having quite a wide range of properties. As above noted, variations in treatment procedure, temperature, etc. also influence the properties of the modified rosin products, so that it is possible, according to the invention, to secure a modified product in which either the acid 'value or melting point is very extensively lowered, or in which both of these properties are simultaneously lowered to a great extent.

In can'ying out the process, the rosin is heated between about 200 C. and 350 C., temperatures above about 250'. 0. being best suited to treatment with the modifying agents herein claimed. For certain purposes and with certain agents, as will further appear, the range is desirably from about 270 C. to about 300 C. Anywhere from a trace or very vsmall percentage, such as .5% or 1%, up to about of the modifying agent is employed, and I have found a particularly advantageous range to be from about 2% to about 10%. In general, the reaction takes place within about 5 hours, although more or less, even down to one half hour under favorable conditions. The efiects of certain varby varying reaction conditions the time may be iations in temperature, percentage of modifying agent and time will be pointed out more fully hereinafter following analysis of examples herein disclosed.

Thorough dispersion of the modifying agent in the rosin is of importance and appropriate control of temperature and time both contribute to bringing about such thorough dispersion. Agitation may also be used as an aid to thorough dispersion.

Another important consideration is that the reaction is preferably carried out in the absence of air, or out of contact with any substantial quantity of air. For this purpose the reaction is desirably carried out in a closed vessel, though not usually under a positive pressure, so that the gases released from the modifying agents (preferably carbonates, sulphides or sulphites), or gases and/or vapors evolved from the reaction mixture during the process, serve to exclude the used, a pressure for instance of from mms.

Hg to about 450 mms. Hg will be found eflfective, although in some cases more or less may be used. Whatever means or procedure is employed, it is of advantage to so conduct the process as to reduce oxygen concentration in the reaction vessel and prevent entrance of fresh air or oxygen to the reaction mixture.

Some more or less general considerations regarding the process should be noted, as follows:

Although the complete mechanism of modification may not be fully understood, it may be mentioned that rosin is an organic isocolloid, i. e., a colloidal system in which the dispersed phase and the dispersion medium are both of the same chemical composition, though present in.

and dispersion medium may be altered. Moreover, the modification process apparently also involves decarboxylation, the extent of which is usually incomplete. Still further, formation of a soap may occur, by reaction of the rosin with the metal of the compound employed as modifying agent. This soap formation may be responsible, in some instances, for at least a part of the reduction in acid value; and in some cases, may further have the effect of holding the melting point relatively high.

In fact, some of the foregoing effects or reactions (particularly with respect to the physical consistency of the modified product) may work in one direction and others in the opposite direction. Thus, when soaps are heated with rosin under certain reaction conditions they may increase the melting point of the rosin. Therefore a partial soap formation during the process may, so to speak, counteract the liquefaction procedure and the end melting point may be the differential result of the liquefying action of the modifying agent and of the solidifying action of a soap formation.

Possibly also non-volatile aggregates or polymers are formed.

In considering the nature of the modifications, it is to be noted that, while somesmall loss in weight may occur by volatiiization (usually not more than about 15-20%), no appreciable fractional or destructive distillation takes place.

With appropriate precautions to avoid distillation the process can usually be carried out without loss of more than or such small loss as does occur usually comprising water, CO2, etc., at least in major part. As a precaution, the temperature should be kept below the boiling or distillation point of the main reaction product,

ized by boiling points all lying within a narrow and relatively high temperature range, as can be demonstrated by subsequent distillation of the modified products. The modified products, for practical purposes, are non-volatile when exposed to the air.

It is of importance in securing various of the foregoing characteristics that the reaction take place without any appreciable concurrent distillation. In addition, the absence of air and/or control of temperature are important in avoiding destructive distillation.

Whatever the exact nature of the chemical, colloidal and/or physical changes which are brought about, in general the treatment provided in accordance with the present invention reduces the acid value of the modified product and also softens or liquefies the material. These changes,

together with others which usually take place, such as imparting drying characteristics to the rosin, and improving film forming properties of the modified products as compared with untreated rosin in the absence of other vehicle solids, for instance, make possible or practicable use of vmy modified rosin products for many purposes EXAMPLES In a table given herebelow, there are reproduced the results of some comparative experiments which were conducted under the same conditions, except for certain designated changes which serve to illustrate differences in properties which may be secured by variations in process.

In all cases the experiments of this comparative series employed 5% of the metal salt and in all cases the treatment was conducted on W wood rosin (Newport Industries), 1,000 gms. of the rosin being heated ina three liter distilling flask, under a pressure of about 400 mms. Hg. The treatment period was 5 hours. The temperature indicated represents a fairly close average maintained throughout the 5 hour treatment period (usually within 10 C. plus or minus).

All temperatures are given in degrees centigrade.

Table of comparatioe experiments Ex. Acid Iodine Melting Consis- No. Temp value value point tency 1 Lithium car- 290 26. 3 168. 3 67 Slightly carbonate. plastic. 2 -.do 320 3.7 178.2 68.5 Do. 3 Sodium sul- 290 72.4 181.5 62 Do.

hide (anydrous). 4 .--do 320 33.8 173.8 Plimtic 5 Sodium sul- 290 91. 7 175. 5 60 Slightly phide (hyplastic drated). 6 do 310 64.7 163.2 Plastic 7 Ammonium 290 112. 2 137.15 56 Slightly sulphite. plastic A (WW wood 169 206. 2 81 Brittle rosin withsolid. out any treatment.) B (Heated 290 130.3 150.8 68 Do.

w i t h o u t agent). C d0 320 97.8 129.1 Plastic.

The designations under the Consistency" column may be further explained and amplified as follows: I

as a three-hourkettle bodied linseed oil, the

viscosity sometimes being down as far as about M on the Gardner scale or even somewhat lower.

' At the bottom of the foregoing table the three examples lettered A, B and C indicate the followperiments, except that no treating agent was employed during the heating, these two differing from each other in reaction temperature.

In determining melting point, the mercury method was used. No melting point determinations were made on plastic or softer products because of the impracticability of securing accurate results.

In determining iodine values, the Wijs method was used.

The inclusion of items A, B and C in the above table will facilitate analysis of the efiects secured by employment of various different modifying agents. The blank experiment B should be compared with various of the numbered experiments conducted at 290; and the blank experiment C should be compared with others of the numbered experiments conducted at 320 (plus or minus 10 0.).

From the table it will be seen that acid value,

melting and consistency may all be extensively going treatment.

and 2) the acid value is very greatly diminished without, however, very substantially reducing the melting point. On the other hand, in some instances the rosin is very extensively softened or liquefied, without, however, reducing the acid value to a great degree. In still further cases, both the acid value and the melting point are very considerably reduced, as is indicated in the results for Example 4 employing sodium sulphide (anhydrous).

The color of the rosin may change as a result of the process. In many cases, products of quite light color are secured, which is of advantage for many purposes, such as in varnishes and other coating compositions. Examples 4, 5 and 6, above, gave quite light products, most of the others being of medium color.

Example 8 A batch of rosin was heated with 5% of lithium carbonate under a pressure of 150 mms. Hg. Initially the temperature was taken up to 280 C. and the reaction mixture maintained at that temperature for about two and one half hours. Thereafter the batch was permitted to drop in temperature and was maintained at about 260 C. to 270 C. for three hours. The batch was again permitted to cool and was maintained at about 240 C. to about 250 C. for an additional period of three hours. Finally the temperature was again raised to 280? C. and maintained for five hours.

The product was of brownish color and was plastic, as defined above.

Certain variations in procedure may be adopted.

For example, instead of using vacuum during the treatment period, other procedure may be adopted with a view to excluding air from the reaction. The form of the reaction vessel employed may be such that gases evolved from the reaction will serve to effectively exclude air, without applying vacuum. Furthermore, certain gases, such as S02, CO2 or nitrogen can be either bubbled through the reaction mass or employed as a blanket on the surface of the batch under- Expedients of this type not only serve to exclude the air from the reaction but may also be utilized for their supplemental effect on the material being treated, this subject being more fully considered in my copending application Serial No. 386,371, filed April 1, 1941, of which the present application is a continuation. It is here further noted that certain features herein disclosed are also disclosed in my prior U. S. applications Serial No; 318,650, filed February 12, 1940 (now Patent No. 2,298,270); Serial No. 359,425 (now Patent No. 2,213,944); and Serial No. 143,786 (now Patent No. 2,189,772).

Moreover, as disclosed in the above mentioned copending applications, still other variations in process may be employed for a number of different purposes, but it is not thought necessary to discuss these fully herein, since reference may be made to the copending applications for that purpose. In passing, however, it is noted that additional treating agents, of a supplemental character, may also be present during the reaction, among which might be mentioned dissolution promoting agents of the type disclosed in my issued Patent No. 2,293,038. Various combinations of modifying agents may also be used for different purposes, 'ncluding combinations of the modifying agents above disclosed, as well as combinations of the modifying agents herein disclosed with agents disclosed in other of my applications mentioned above as well as hereinafter.

It is further to be noted that in general increasing any one or all of the variables: namely, temperature, time of treatment and percentage of modifying agent, increases the extent of modification. It will be understood that the foregoing is a general rule normally applicable within the ranges of operation above indicated, although, as to at least some variables, there may be limits beyond which the general rule does not apply. For instance, excessive increase in temperature may substantially alter the character of the process. On the other hand, in instances where a soap forming metal is present in the modifying agent, excessive increase in percentage of modifying agent may not yield as soft a product as a lower percentage of the modifying agent.

In considering the starting material on which the process may be employed, it is first noted that the process brings about changes both of colloidal and also of a chemical nature. It is important, however, to bear in mind that the process essentially involves a reaction with the rosin molecule, that is, with the type of molecules of which the basic constituents of natural rosin are composed. Therefore, while rosin itself, such as gum or wood rosins, represents perhaps the most important starting material to which the process is adaptable, it is noted that the process may be employed on rosin which has been pretreated in various ways, or on mixed or chemically condensed materials incorporating rosin, since the reaction will take place wherever the rosin molecule is present, provided, of course, that the physical or chemical state or environment of the rosin molecule is not such as to prevent the reaction from taking place.

It may also be mentioned that there are other natural resins, such as copals, which act similarly to rosin by treatment in accordance with this invention. In fact, the reaction may be carried out on any of the natural resins containing high molecular resin acids. Therefore, wherever any such other natural resin behaves similarly to rosin, it is herein considered as an equivalent.

Copals are fossil gums which have to be fused before becoming soluble in organic solvents and miscible with fatty oils. When copals are used in the present process, they should be employed in the fused state.

The modified product of this invention may if desired, be subject to other treatment, depending upon the use for which it is intended. Thus, for example, the modified products may bevulcanized with sulphur. The modified resin products secured in accordance with the foregoing, may be vulcanized as such, or in solutions. such as varnish solutions, in the latter case with sulphur chloride).

Further, they may be converted intoemulsions and used for various purposes in that form.

In the event sulphur or other sulphur-like vulcanizing agents are used, vulcanization, for certain purposes, is desirably carried out at temperatures between about C. and 200 C. For purposes where vulcanization is to be effected at lower temperatures, for instance, at room temperature, sulphur chloride, or similarly acting vulcanizing agents, should be used. In instances where the vulcanization is carried out in :1 varcapable of releasing a nish solution, the sulphur chloride treatment is especially practical.

As is mentioned in my copending application Serial'No. 388,371, filed April 1. 1941. the modified rosin products may be subject to still other supplemental treatments, such for instance as esterificatlon, as by treating with glycerine or other polyhydric alcohols, such as glycols, pentaerythrltol, mannitol, sorbitol, etc.

The vulcanized liquefied resin products made in accordance with the invention have valuable properties for a number or purposes including the making of protective coatings, some of these vulcanized products being. useful as plasticizers for coating compositions and plastics.

It is noted that in copending applications filed concurrently herewith, certain other moditying agents are claimed in the treatment of rosin: See applications Serial Nos. $61,787; 461,790; 481,791; 461,793 to 461,797 inclusive; and 461,800. Other rosin treatment is also disclosed in oopending application 447,439 filed June 17, 1942.

I'claim: a

1. A process for making a modified and sortened rosin product from hard and brittle rosin,

which process comprises incorporation in the rosin 01' up to 30% of a salt having an anion capable of releasing a gas other than oxygen under the conditions of the process, and selected from the class consisting oi carbonates, sulphides and sulphites iormed with a member of the cation class consisting of the alkali metals and ammonia, and heating the mixture out 01 contact with the atmosphere between about 250 C. and 350 C., but-not above the temperature at which appreciable destructive distillation occurs under the conditions of the treatment, the heating being continued until the resultant mixture, when cooled, is softened as compared with the same rosin treated under the same conditions but without the modifying agent, but the extent oi softening not being beyond that yielding a semisolid plastic mass displaying cold fiow properties, the time of treatment iurther being sufiicient to reduce the acid value or the rosin as compared with the acid value of the same rosin heated to the same temperature under the same treatment conditions but without a modifyi a ent.

2. A process for making a modified and softened rosin product from hard and brittle rosin, which process comprises incorporation in the rosin of upto or a salt having an anion gas other than oxygen under the conditions of the process, and selected from the class consisting of carbonates, sulphides and sulphites formed with a memberof the cation class consisting of the alkali metals and ammonia, and heating the mixture out of contact with the atmosphere between about 250 C. and 350 0., but not above the temperature at which appreciable destructive distillation occurs under the conditions of the treatment, the heating being continued until the resultant mixture, when cooled, is softened as comparedwith the same rosin treated under the same conditions but without the modifying agent, but the extent of softening not being beyond that yielding a semisolid plastic mass displaying cold flow properties. the time of treatment further being sufiicient to reduce the acid value of the rosin as compared with the same rosin-heated to the same temperature under the same treatment conditions but without a modifyin ent.

3. A process in accordance with claim 2 in which the heating is continued at least until the resultant mixture. when cooled, has cold flow consistency.

4. A process in accordance with claim 2 in which the quantity of salt employed is from 2% 5. A process in accordance with claim 2 which said salt is an alkali metal carbonate.

6. A process in accordance with claim 2 which said salt is an alkali metal sulphide. '7. A process in accordance with claim 2 which said salt is an alkali metal sulphite.

8. A process in accordance with claim 2 which said salt is a lithium salt.

9. A process in accordance-with claim 2 which said salt is a sodium salt.

10. A process in accordance with claim 2 which said salt is an ammonium salt.

11. A process in accordance with claim 2 which said salt is lithium carbonate.

12. A process in accordance with claim 2 which said salt is sodium sulphide.

13. A process in accordance with claim 2 which said salt is ammonium sulphite.

15. A process in accordance with claim 2 inwhich the heating is effected under vacuum.

miszrb sum. 

